Textile treating chemical and process of making it



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Jersey No Drawing. Application May 6, 1942,

" Serial No. MLii'Zii 8 Claims. (Cl. 260-295) This invention relates'towater-soluble reaction products of a tertiary amine with the productformed from the reaction of a nitrile with a long chain fatty acidchloride and formaldehyde, said products being valuable in treatingtextile fabrics. The invention also relates to the process of mak ingsuch products and is a continuation in part of my copending applicationSerial Number 392,937 filed May 10, 1941.

According to the process of the present invention an organic nitrile isreacted with a long chain fatty acid chloride having a carbon chain ofmore than about 9 carbon atoms in the presence of formaldehyde. Thereaction product so formed is then reacted with a tertiary'amine such aspyridine although I'have also found that the nitrile, acid chloride,formaldehyde and tertiary amine may be reacted all together to givesatisfactory Water-soluble products. The reaction may be carried out attemperatures ranging from 50 C. or 60 C. up to 1l0-C'.'or slightlyhigher for periods of time varying between 30 minutes to about twentyhours. As tertiary amines I. prefer to employ pyridine, qulnoline,trimethyl amine, alpha picoline or technical mixtures such as pyridinebases which contain picoline and lutidine in addition to pyridine.

The water-soluble products of the present invention are admirably suitedfor treating textile fabrics to which they impart a soft suede hand.Furthermore, it has been found that if a cotton. rayon, acetate or woolfabric which has been treated with a 1% to 20% solution of thewatersoluble products of the present invention is heated at an elevatedtemperature of above 100 (2. and

preferably between 140 C. and 170 0., the product becomes fixed on thefabric and imparts thereto an excellent waterrepellent finish.

As the nitrile component of the present invention I may employmalononitrile, succinonitrile. acetonitrile, acrylonitrile,propionitrile, cyclic and heterooyclic nitriles such as benzonitrile,nicotinonitrile and complex nitriles such as methyleneaminoacetonitrileand the like. Such nitriles contain less than 9 carbon atoms. As theacid chloride component I may employ, for example, decanoyl chloride,dodecanoyl chloride, palmltyl chloride (hexadecanoyl chloride), stearylchloride (octadecanoyl chloride), behenyl chloride (docosanoyl chloride)and the like, or mixtures thereof.

The following examples are given to illustrate the products and processof the present invention., All proportions are given in parts by weight.

r be incorporated in the acid chlorides.

Example 1.- -66.5 parts of palmityl chloride, 25 parts of benzonitrile,14.6 parts of paraformaldehyde and 1 part of zinc chloride were heatedtogether with constant agitation at '15-80 C. for 21 hours. The productwas then cooled to room temperature and 19.2 parts of pyridine wereslowly added with agitation. The temperature rose to 55 C. during theaddition and the product then heated at -'l5 C. for 1% hours, then for15 hours at 65 C. The material was readily soluble in water to givestrongly foaming solutions. At room temperature it was a hard, ratherhigh melting, light yellow wax. I

Example 2.2l4.5 parts of palmityl chloride, 55 parts of propionitrile,45 parts ofparaformaldehy'de, and 2.7 parts of zinc chloride were heatedtogether with rapid agitation at 77 C. for 20 hours. The reaction wasthen allowed to cool to about 30 C. and 79 parts of pyridine were slowlyadded. The temperature rose during this addition to about 55 C. and theproduct was then heated at 6065 c. for 2 /2 hours. The\product wassomewhat soft and Wm at room temperature. It was readily soluble inwater to give strongly foaming solutions.

In the process of the present invention it is possible to carry on thereaction in the presence of the tertiary amine.

Example 3.19.5 parts of methyleneaminoaceparts of pyridine were heatedto obtain a solution of the nitrile and a suspension of the paraform inthe pyridine. 86 parts of stearyl chloride were then added slowly over aperiod of 20 minutes maintaining the temperature below 100 C. When allof the, acid chloride had been added the material was viscous and clear.It was then heated at 60-65 C. for 1 hour. The product at roomtemperature was a hard, light yellow wax which was readily soluble inwater to form strongly foe solutions.

The materials of the present invention when applied to cotton fabrics,dried and baked, give water repellent fabrics having standard sprayratings of from 90 to 95. In order to increase the initial rating to100, small amounts of wax may This is exemplified in the followingexample as well as the use of an inert diluent which may be presentduring the reaction.

Example 4.=-- parts of stearic acid (a grade known to the trade as HardHyodol acids); 25 parts of candelilla wax and 20 parts of phosphorustrichloride were heated at 60 to C.

'65 for 4 hours. The resulting acid chloride mixture was decanted fromthe lower phosphorous acid layer. 23 parts ofmethyleneaminoacetonitrile, parts of paraformaldehyde, 45 parts ofpyridine and parts of dloxan were heated to about 80 C. to obtainsolution of the nitrile. The acid chlorides as formed above were thenadded slowly with rapid agitation over a period of about to minutesmaintaining the temperature below 100 C. When all of the acid chlorideshad been added the viscous mixture was heated at -80 C. for 1 hour withagitation. At room temperature the material was a hard, light brown waxwhich dissolved readily in water and in 1% to 10% solution at 70-80 C.gave clear, opalescent dispersions.

In employing the compounds of the presen invention on textile fabrics aswater repellents I have found that the preferable procedure is todissolve the material in water to form about a 5% solution of solids,although from 1% to 10% may be used if desired. The impregnated fabricis dried at a relatively low temperature (below 100 C.) for a shorttime, then baked at above 100 C. and preferably at 120 C. to 170 C. forfrom 1 to 20 minutes.

As an illustration, the materials formed as described in Examples 8 and4 were dissolved in water to form a solution containing 6% solids. Anolive drab dyed mercerized poplin was impregnated with the solutions,squeezed between rubber rolls to remove the excess solution, driedpellency obtained from such nitriles containing less than 9 carbon atomsis consistently high, which is unexpected since long chain compounds asa rule produce greater hydrophobic tendencies than shorter chaincompounds. It is probable that more complete reaction with the textileflhers is obtained. The chemical structure of the water.

at about -100 C. in a current of air and baked at 160-l65 C. for 2minutes. The treated fabric was given a preliminary soaping in soap andwater at 60 C. to remove unreacted compounds, then rinsed and dried.Standard spray readings were taken on the fabric according towell-established methods as outlined in my 00- pending applicationSerial Number 392,937 filed May 10, 1941. The fabric treated with theproduct of Example 3 gave a spray rating of which after three standarddry cleanings with petroleum naphtha was only reduced to 80. The fabrictreated with the product of Example 4 gave a spray rating of which afterthree dry cleanings was reduced to 80.

In contrast to the products of my copending application Serial Number392,937 which are produced from formaldehyde, long-chain acid chlorides,nitriles of more than 9 carbon atoms and a tertiary amine, the improvedproducts, obtained from nitriles such as methyleneaminoacetonitrile, aresimultaneous reaction products and may be obtained by adding the acidchloride to the initial mixture of formaldehyde, tertiary amine andnitrile. Furthermore, the degree of water-re- 2. The process whichcomprises heating at a temperature of from about 50 C. to about C.formaldehyde, 9. nitrile containing less than 9 carbon atoms, a tertiaryamine and adding thereto an acid chloride containing a chain of morethan 9 carbon atoms; and continuing heating until a reaction product hasbeen obtained which is readily soluble in water.

3. The process of claim 2 wherein the formaldehyde, nitrile, acidchloride and tertiary amine are heated in the presence of an inertdiluent.

4. The process which comprises heating formaldehyde,methyleneaminoacetonitrile, pyridine and octadecanoyl chloride at anelevated temperature until a reaction has occurred to yield awater-soluble product.

5. The process which comprises heating formaldehyde,methyleneaminoacetonitrile, a, tertiary amine and an acid chloridehaving a carbon chain of more than 9 carbon atoms at an elevatedtemperature until a reaction has occurred to yield a water-solubleproduct.

6. The process which comprises heating formaldehyde,methyleneaminoacetonitrile, a tertiary amine, and the acid chloride,obtained from a mixture of palmitic acid and stearic acids andcandelilla wax until a reaction product has been obtained which issoluble in water.

JOHN B. RUST.

